(1,3-di-(2-pyridyl)-2-azaallyl)2Fe | 1133438-00-2

• 分子结构分类: 有机化合物 - 有机杂环化合物
• 英文名称: (1,3-di-(2-pyridyl)-2-azaallyl)2Fe
• 英文别名: (1,3-di-(2-pyridyl)-2-azaallyl)₂Fe；(smif)₂Fe；(1,3-di(2-pyridyl)-2-azapropene(1-))2Fe；((2-py)CHNCH(2-py))2Fe；(smif)2Fe
• CAS: 1133438-00-2
• 化学式: C₂₄H₂₀FeN₆
• 分子量: 448.31
• InChiKey: ZGVJLWGFLRGXCB-YJCYQSLBSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
  None
• 可旋转键数：
  None
• 环数：
  None
• sp3杂化的碳原子比例：
  None
• 拓扑面积：
  None
• 氢给体数：
  None
• 氢受体数：
  None

反应信息

• 作为反应物：
  描述：

  (1,3-di-(2-pyridyl)-2-azaallyl)2Fe 以 四氢呋喃 、 氘代乙腈 为溶剂， 生成 [(smifH)(smif)Fe]BF4
  参考文献：
  名称：

  （smif）2 M n（n = 0，M = V，Cr，Mn，Fe，Co，Ni，Ru; n = +1，M = Cr，Mn，Co，Rh，Ir; smif = 1,3-二-（2-吡啶基）-2-氮杂烯丙基）

  摘要：

  已经制备了一系列具有三齿配体smif的Werner配合物，即1,3-二-（2-吡啶基）-2-氮杂烯丙基。（smif）2 M（1 -M; M = Cr，Fe）的合成通过用2处理M（NSiMe 3）2（THF）n（M = Cr，n = 2; Fe，n = 1）完成当量的（smif）H（1,3-二-（2-吡啶基）-2-氮杂丙烯）; 类似地制备邻甲基化的（o Mesmif）2 Fe（2 -Fe）和（o Me 2 smif）2 Fe（3 -Fe）。MX 2的复分解具有2当量的Li（smif）或Na（smif）的变体生成1- M（M = Cr，Mn，Fe，Co，Ni，Zn，Ru）。将VCl 3（THF）3与2 Li（smif）进行复分解，使Na / Hg还原当量，得到1- V，而在NaBPh 4存在下，2 Na（smif）和IrCl 3（THF）3发生[[（ smif）2 Ir] BPh 4（1 + -Ir）。电化学实验导致AgOTf将1

  DOI：

  10.1021/ic200376f
• 作为产物：
  描述：

  二甲基吡啶胺 以 乙醚 、 氘代苯 为溶剂， 反应 32.0h， 生成 (1,3-di-(2-pyridyl)-2-azaallyl)2Fe
  参考文献：
  名称：

  C–C Bond Formation and Related Reactions at the CNC Backbone in (smif)FeX (smif = 1,3-Di-(2-pyridyl)-2-azaallyl): Dimerizations, 3 + 2 Cyclization, and Nucleophilic Attack; Transfer Hydrogenations and Alkyne Trimerization (X = N(TMS)₂, dpma = (Di-(2-pyridyl-methyl)-amide))

  摘要：

  Molecular orbital analysis depicts the CNCnb backbone of the smif (1,3-di-(2-pyridy1)-2-azaally1) ligand as having singlet diradical and/or ionic character where electrophilic or nucleophilic attack is plausible. Reversible dimerization of (smif)Fe{N(SiMe3)(2)} (1) to [{(Me3Si)(2)N}Fe](2)(mu-K-3,K-3-N,py(2)-smif,smif) (2) may be construed as diradical coupling. A proton transfer within the backbone-methylated, and o-pyridine-methylated smif of putative ((b)Me(2)(0)Me(2)smif)Fe-N(SiMe3)(2) (8) provides a route to [{(Me3Si)(2)N}Fe](2)(mu-K-4,K-4-N,py(2),C-(Me-b,(CH2)-C-b,Me-0(2)(smif)H))(2) (9). A 3 + 2 cyclization of ditolyl-acetylene occurs with 1, leading to the dimer [{2,5-di(pyridin-2-yl)-3,4-di-(p-tolyl-2,5-dihydropyrrol-1-ide)}FeN-(SiMe3)(2))(2) (11), and the collateral discovery of allcyne cyclotrimerization led to a brief study that identified Fe(N(SiMe3)(2)(THF) as an effective catalyst. Nucleophilic attack by (smif)(2)Fe (13) on 'BuNCO and (2,6-Pr2C6H3)NCO afforded (RNHCO-smif)(2)Fe (14a, R = 'Bu; 14b, 2,6-' PrC6H3). Calculations suggested that (dpma)(2)Fe (15) would favorably lose dihydrogen to afford (smif)(2)Fe (13). H-2-transfer to allcynes, olefins, imines, PhN=NPh, and ketones was explored, but only stoichiometric reactions were affected. Some physical properties of the compounds were examined, and X-ray structural studies on several dinuclear species were conducted.

  DOI：

  10.1021/ic302783y

文献信息

• Frazier, Brenda A.; Wolczanski, Peter T.; Lobkovsky, Emil B., Journal of the American Chemical Society, 2009, vol. 131, p. 3428 - 3429
  作者：Frazier, Brenda A.、Wolczanski, Peter T.、Lobkovsky, Emil B.、Cundari, Thomas R.

  DOI：——

  日期：——